Bioinspired Metal-Ligand Networks with Enhanced Stability and Performance: Facile Preparation of Hydroxypyridinone (HOPO)-Functionalized Materials

Declan P Shannon; Kenneth Cerdan; Minseong Kim; Matthew Mecklenburg; Judy Su; Yueyun Chen; Matthew E Helgeson; Megan T Valentine; Craig J Hawker

doi:10.1021/acs.macromol.4c02250

Bioinspired Metal-Ligand Networks with Enhanced Stability and Performance: Facile Preparation of Hydroxypyridinone (HOPO)-Functionalized Materials

Macromolecules. 2024 Dec 6;57(24):11339-11349. doi: 10.1021/acs.macromol.4c02250. eCollection 2024 Dec 24.

Authors

Declan P Shannon^{1

2}, Kenneth Cerdan^{3

4}, Minseong Kim^{1

2}, Matthew Mecklenburg⁵, Judy Su⁵, Yueyun Chen^{5

6}, Matthew E Helgeson⁴, Megan T Valentine³, Craig J Hawker^{1

7

2}

Affiliations

¹ Materials Department, University of California Santa Barbara, Santa Barbara, California 93106-5050, United States.
² Materials Research Laboratory, University of California Santa Barbara, Santa Barbara, California 93106-5121, United States.
³ Department of Mechanical Engineering, University of California, Santa Barbara, Santa Barbara, California 93106-5070, United States.
⁴ Department of Chemical Engineering, University of California, Santa Barbara, Santa Barbara, California 93106-5080, United States.
⁵ California NanoSystems Institute, University of California, Los Angeles, California 90095, United States.
⁶ Department of Physics and Astronomy, University of California, Los Angeles, California 90095, United States.
⁷ Department of Chemistry & Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106-9510, United States.

Abstract

Bioinspired hydroxypyridinone (HOPO)functionalized materials are shown to display a remarkable capacity for stability and for chelating a wide array of metal ions. This allows for the synthesis of multifunctional networks with diverse physical properties when compared to traditional catechol systems. In the present study, we report a facile, one-pot synthesis of an amino HOPO ligand and simple, scalable incorporation into PEG-acrylate based networks via active ester chemistry. This modular network approach allows for fabrication of patterned HOPO containing networks which can chelate a range of metal ions, such as transition metals (Fe³⁺) and lanthanides (Ho³⁺, Tb³⁺), leading to modulation of mechanical, magnetic, and fluorescent properties. Moreover, networks with tailored, heterogeneous properties can be prepared through localization of metal ion incorporation in 3-dimensions via masking techniques, creating distinctly soft, hard, magnetic, and fluorescent domains.